KR100426416B1 - Additive for synthetic resin - Google Patents

Abstract

The present invention relates to a synthetic resin additive having an antifogging property near an inner surface of an agricultural coating material and which can impart excellent antifogging persistence.

Fluorine-containing compound (R ^f -QO- (AO) _n -R (R ^f : polyfluoro aliphatic hydrocarbon group having 1 to 22 carbon atoms, Q: alkylene group having 1 to 5 carbon atoms, n: integer of 1 to 100, A : Synthetic resin additive containing R: a hydrogen atom, a C1-C18 hydrocarbon group, etc., such as a C2-C4 alkylene group.

Description

Synthetic Resin Additives {ADDITIVE FOR SYNTHETIC RESIN}

In recent years, greenhouse cultivation and tunnel-type greenhouse cultivation are vigorously performed to increase productivity and marketability of useful plants. This is to cultivate useful, semi-promoting, or inhibiting cultivation of useful plants under coating with a coating material such as a synthetic resin film.

Synthetic resins (such as vinyl chloride resins), which are currently used for agricultural coating materials, contain antifogging agents, which are a type of surfactant. This is to accelerate the flow of water droplets on the inner surface of the coating material (the surface of the inside of the greenhouse. The same applies hereinafter) to increase the amount of incident sunlight.

However, under the coating of the coating material containing such an antifogging agent, the temperature difference between the coating material and the outside becomes large. Therefore, fog often occurs near the inner surface of the coating material.

As a technique for improving such defects, a method of incorporating a fluorine-based surfactant that improves antifogging property (Japanese Patent Laid-Open No. 5-72942) has been proposed.

However, according to the experiments of the present inventors, it was found that not all fluorine-based surfactants exhibit antifogging properties, and even a compound exhibiting antifogging properties may have an excellent adverse effect on the antifogging persistence of the film.

An object of the present invention is to provide a synthetic resin additive which has the ability to suppress the occurrence of fog in the vicinity of the inner surface of the coating material when added to an agricultural coating material (fog prevention property) and which has excellent antifogging persistence.

The present invention relates to a synthetic resin additive. In detail, when added to an agricultural coating material made of synthetic resin film, it has the ability to suppress the fog generated on the inner surface of the coating material (this ability is called an antifogging property) and also has an excellent laver. It relates to a resin additive that has the ability to exert an anti-glare effect over a long period of time (this ability is called anti-fog persistence).

The present invention provides a synthetic resin additive containing a fluorine-containing compound represented by the following formula (1).

R ^f -Q-O-(A-O) _n -R

(In the meal,

R ^f : C1-C22 polyfluoroalkyl group

Q: C1-C5 alkylene group

n: integer of 1-100

A: when at least one hydrogen atom of an alkylene group having 2 to 4 carbon atoms or an alkylene group having 2 to 4 carbon atoms is substituted with a monovalent aromatic hydrocarbon group, an alkoxy group or a phenoxy group, and n is 2 to 100; Each of A may be the same or different)

The present invention also provides an agricultural coating material comprising a film of a synthetic resin containing the above fluorine-containing compound but no antifogging agent.

The fluorine-containing compound of the present invention is represented by the following formula (1).

[Formula 1]

R ^f -Q-O-(A-O) _n -R

Wherein R ^f is a polyfluoroalkyl group (hereinafter referred to as R ^f group) having 1 to 22 carbon atoms. R ^f is a group in which two or more hydrogen atoms in the alkyl group are substituted with fluorine atoms.

Although carbon number of R <^f> group is 1-22, 1-16 are preferable and 6-14 are especially preferable. R ^f groups can be of a fluorine atom is (R ^f number of fluorine atoms in the group) / case represented by (R ^f equal to hydrogen atoms of the alkyl group having a carbon number of corresponding groups) × 100 (%) 60% or more are preferred for the 80 At least% is particularly preferred. Moreover, a linear structure or a branched structure may be sufficient as R <^f> group, and especially linear structure is preferable. In the case of a branched structure, it is preferable that a branched part is a C1-C3 short chain and exists in the terminal part of R <^f> group.

The R ^f group is a perfluoroalkyl group (hereinafter referred to as R ^F group) and a straight chain structure is preferable. The R ^F group is a group in which all of the hydrogen atoms in the alkyl group are substantially substituted with fluorine atoms. That is, the group in which the R ^F group is represented by F (CF ₂ ) _m − (m is an integer of 1 to 18) is preferable. 4-16 are preferable and, as for m, 6-14 are especially preferable.

The linear group R ^f group can be obtained by adding tetrafluoroethylene to a C ₂ F ₅ I by teromerization reaction. The branched R ^f group can be obtained by oligomerizing a fluorine-containing monomer such as tetrafluoroethylene or hexafluoropropylene with a catalyst such as KF or CsF.

The fluorine-containing compound may be a mixture of two or more kinds of compounds having different carbon atoms in the R ^f group. In particular, as a main component a fluorine-containing compound of the R ^f group having the carbon number of 6 to 14, and preferably a mean carbon number of 8-10 in particular is a mixture of R ^f groups.

Q in a fluorine-containing compound is an alkylene group having 1,2,3,4 or 5 carbon atoms. 2, 3 or 4 is preferable and, as for carbon number of Q, 3 or 4 is especially preferable.

The fluorine-containing compound in which Q is an alkylene group having 3 or 4 carbon atoms is a compound having excellent chemical stability and heat resistance even in various environments, especially when used as a synthetic resin additive.

As Q, an ethylene group, trimethylene group, tetramethylene group, propylene group (-CH (CH ₃ ) CH _2- ), butylene group (-CH (CH ₃ ) CH ₂ CH _2- , -CH ₂ CH (CH ₃ ) CH _2- , -CH (CH ₃ ) CH (CH ₃ )-, and the like. In addition, when Q has an asymmetric structure (for example, a propylene group), R <^f> group may couple | bond to any bond position.

N in a fluorine-containing compound represents the integer of 1-100, and the integer of 2-50 is preferable. Even when the fluorine-containing compound of the present invention is a mixture of two or more compounds having different n numbers, the average value of n is preferably in the range of 1 to 50, and particularly preferably in the range of 2 to 30.

A in the fluorine-containing compound is a group in which at least one hydrogen atom of an alkylene group having 2 to 4 carbon atoms or an alkylene group having 2 to 4 carbon atoms is substituted with a monovalent aromatic hydrocarbon group, an alkoxy group or a phenoxy group. And the like - preferably an ethylene group, a tetramethylene group, a propylene _{group, -CH (C 6 H 5)} CH 2 -, -CH (CH 2 OR 1) CH 2. When A has an asymmetric structure (for example, a propylene group), the direction is not limited. However, R <^1> represents a C1-C10 alkyl group and R <^1> is a methyl group, a butyl group, and 2-ethylhexyl group.

When n is 2-100, these two or more A may be same or different, respectively. When different, it is preferable that A is two types or three types, and it is especially preferable that it is two types. It is preferable that 1 type or 2 types of A in a fluorine-containing compound exist especially, and only an ethylene group only, a propylene group, or two types of ethylene group and a propylene group are preferable.

(AO) _n is an oxyalkylene group or polyoxyalkylene group obtained by ring-opening addition reaction of a cyclic ether.

The cyclic ether is preferably a compound containing a 3 to 5 membered cyclic ether group having one oxygen atom in the ring, and more preferably a compound (monoepoxide) having one 3 membered cyclic ether group. Especially preferably, they are alkylene oxide of 2, 3 or 4 carbon atoms.

Examples of the cyclic ether include ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, isobutylene oxide, oxetane, methyl oxetane, phenylglycidyl ether, tetrahydrofuran and styrene oxide. And alkyl glycidyl ethers. As alkylglycidyl ether, methylglycidyl ether, butylglycidyl ether, 2-ethylhexyl glycidyl ether, etc. are mentioned.

Preferred cyclic ethers are ethylene oxide, propylene oxide or tetrahydrofuran. On the other hand, A formed by ring opening of tetrahydrofuran is a tetramethylene group.

It is preferable to use 1 or more types of cyclic ether. When using 2 or more types of cyclic ethers, the mixture of 2 or more types of cyclic ethers may be used for reaction, and 2 or more types of cyclic ethers may be used for sequential reaction.

R in a fluorine-containing compound represents a hydrogen atom, a C1-C18 alkyl group, or a C1-C18 acyl group.

When R is a C1-C18 alkyl group, a methyl group, an ethyl group, n-propyl group, n-butyl group, and n-pentyl group are preferable. When R is a C1-C18 acyl group, a C1-C10 acyl group is preferable and a C1-C6 acyl group is especially preferable. Moreover, this acyl group may have functional groups, such as a carboxyl group. As R, a hydrogen atom or a methyl group is preferable, and a hydrogen atom is particularly preferable.

Specific examples of the fluorine-containing compound (however, examples of the compound of which the R ^f group is C ₈ F _17- ) include the following compounds, but are not limited thereto. However, although the part corresponding to R <^F> group in a following compound may be linear structure or a branched structure, a linear structure is preferable. Moreover, when the polyoxyalkylene chain containing two or more types of oxyalkylene groups exists, these ordering methods may be block or random. The (C ₃ H ₆ O) moiety represents an oxypropylene group and represents [CH (CH ₃ ) CH ₂ O] or [CH ₂ CH (CH ₃ ) O]. In addition, the (C ₄ H ₈ O) moiety represents (CH ₂ CH ₂ CH ₂ CH ₂ O) which is a ring-opening compound of tetrahydrofuran.

In the present invention, the fluorine-containing compounds may be used alone, or two or more kinds thereof may be used in combination.

The fluorine-containing compound of the present invention is obtained by ring-opening addition reaction of a cyclic ether to R ^f QOH.

The synthesis method of R ^f QOH (where R ^f = R ^F ) is as follows.

In the case of R ^F CH ₂ OH having 1 carbon number of Q, ethylene is added to perfluoroalkyl iodine (R ^F I) obtained by teromerization and alkali treatment is performed to perfluoroalkylethylene (R ^F CH = CH ₂ ). Get There is a method of oxidizing this to obtain a perfluoroalkane carboxylic acid (R ^F COOH) and reducing this to NaBH ₄ .

Examples of the method for synthesizing R ^F (CH ₂ ) ₂ OH having 2 carbon atoms in Q include a method obtained by inserting ethylene into R ^F I and replacing terminal iodine with a hydroxyl group.

The method for synthesizing R ^F (CH ₂ ) ₃ OH having 3 carbon atoms in Q includes a method obtained by adding allyl alcohol to R ^F I and then replacing iodine with hydrogen with a reducing agent.

The method for synthesizing R ^F (CH ₂ ) ₄ OH having 4 carbon atoms in Q includes a method obtained by adding 3-butene-1-ol to R ^F I and then replacing iodine with hydrogen with a reducing agent.

Further, while heating was added to a given radical initiator in synthesis of the ^{_{R F CH 2 CH 2 CH 2}} (OH) of the isomer of the compound CH ₃ is a large amount of an ethanol solvent for the R ^F CH = CH _2, from the carbon number of 4 And a method obtained by stirring and adding ethanol in a radical addition reaction.

The method for synthesizing R ^F (CH ₂ ) ₅ OH having 5 carbon atoms of Q includes a method obtained by adding 4-pentene-1-ol to R ^F I and then replacing iodine with hydrogen as a reducing agent.

When ring-opening addition-reacting two or more types of cyclic ether, these may be mixed, and may be reacted sequentially. When using only one type of cyclic ether, when using two or more types, all may be put into a reaction system collectively, and may be added to a reaction system gradually.

Fluorine-containing compounds can usually be produced by reacting a mixture of cyclic ethers with R ^f QOH in the presence of a catalyst. Moreover, reaction can also be performed, adding a cyclic ether gradually to a reaction system. As the catalyst used, an alkali catalyst such as KOH, NaOH, or CsOH can be generally used. In the case of R ^f QOH, metal complex catalysts such as acid catalysts such as BF ₃ and complex metal cyano compound complexes are preferable.

In the case of R ^f QOH, side reactions of deHF may occur under strong alkaline conditions, and it is preferable to use a mild alkali catalyst such as a three-way catalyst of NaBH ₄ / NaI / I ₂ or the acid catalyst or the metal complex catalyst. In the case of acid catalysts, if the acidity of the catalyst is too strong, hydrogen atoms bonded to the neighboring carbon atoms of the carbon atoms to which the fluorine atoms are bonded in the R ^f group may be released. You may use a dilution solvent accordingly. Examples of the dilution solvents include ether solvents such as slime, diglyme, trilime and methyl t-butyl ether.

The reaction temperature at which the cyclic ether is added is preferably -20 to + 180 ° C, particularly preferably 0 ° C to 130 ° C. When using a low melting dilution solvent, it is preferable to react at a temperature lower than (solvent melting point +20 degreeC) in consideration of the internal pressure rise.

Various characteristics can be adjusted as a fluorine-containing compound by terminally modifying the terminal hydroxyl group of the polyoxyalkylene chain thus obtained, such as esterification and alkylation.

Examples of the organic carboxylic acid used for esterification include monovalent carbohydrates such as acetic acid, propionic acid, butanoic acid, 2-ethylhexanoic acid (octylic acid), 3,5,5-trimethylhexanoic acid (isononanoic acid), oleic acid and stearic acid. Acids, esters of these carboxylic acids and low melting alcohols and acid anhydrides can be used. Moreover, divalent carboxylic acid, carboxylic acid ester, and its acid anhydride, such as oxalic acid, succinic acid, maleic acid, fumaric acid, and phthalic acid, can also be used.

The esterification is carried out by adding these carboxylic acids, carboxylic acid esters or acid anhydrides to the hydroxyl group-terminated fluorine-containing compound polyoxyalkylene compound, and without a catalyst or a trace acid catalyst such as paratoluenesulfonic acid or sulfuric acid or potassium hydroxide or sodium hydroxide. Stirring while heating in the presence of an alkali catalyst. It is then carried out by distilling off dehydration, dealcohol or unreacted acid.

Alkylation includes a method of reacting with monohaloalkyl under strong alkali conditions, a method using alkyl sulfuric acid, and the like. In order to suppress the elimination reaction of fluorine, the reaction using alkylating agents, such as an alkyl sulfuric acid, is preferable.

The fluorine-containing compound thus obtained is preferably purified by acid treatment with sulfuric acid, phosphoric acid or the like, adsorption treatment with synthetic magnesium, activated clay, activated carbon or the like.

The amount of R ^f QOH that is an initiator in the reactor depends on the amount of cyclic ether compound added. Considering the stirring conditions of the reactor, it is preferable to add 1/10 or more of the reactor contents. Considering the volumetric efficiency, the volume ratio is preferably 80 to 95% after the addition of the cyclic ether, but is not particularly limited thereto.

The compounding quantity of a fluorine-containing compound to synthetic resin can be suitably determined according to the kind etc. of the fluorine-containing compound mix | blended. 50-100 mass parts is preferable with respect to 100 mass parts of synthetic resins, and, as for the compounding quantity of a fluorine-containing compound, 70-99 mass parts is especially preferable.

The agricultural coating material of this invention consists of a synthetic resin film containing the said fluorine-containing compound but without the antifog.

In the case where the fluorine-containing compound of the present invention is added to a synthetic resin which is a material of an agricultural coating material, 0.01 part by mass or more is preferred per 100 parts by mass of synthetic resin (but no plasticizer is included in the calculation. Although an upper limit is not restrict | limited strictly, when it mix | blends too much, there exists a possibility that it may generate bleed out and turbidity, and it is usually enough at 2.0 mass parts or less. As for the compounding quantity of a fluorine-containing compound, 0.02-1.0 mass part is especially preferable per 100 mass parts of synthetic resins.

Synthetic resins, which are materials of synthetic resins and agricultural coating materials, include film-forming thermoplastic synthetic resins in addition to thermosetting resins and thermoplastic resins for molding. Specifically, monomers such as vinyl chloride, ethylene, propylene, acrylic esters, methacrylic esters or the like, or copolymers thereof, or monomers copolymerizable with one or more of these monomers (for example, vinyl acetate, vinylidene chloride, etc.) And copolymers of fluorine-containing resins, polyesters, polyamides, or the like.

Among them, for film, vinyl chloride resins (ie, copolymers containing 50% by mass or more of polymerized units of polyvinyl chloride and vinyl chloride) and ethylene-based resins (i.e., polyethylene) from the viewpoint of weather resistance, light transmittance, economy, and strength. And copolymers containing 50% by mass or more of polymerized units of ethylene), and polyvinyl chloride is particularly preferable.

In the synthetic resin of the present invention, conventional various additives such as a plasticizer, a lubricant, a heat stabilizer, an antistatic agent, an ultraviolet absorber, a pigment dye, a heat retention agent, and the like can be blended in conventional amounts.

Examples of the plasticizer include phthalic acid derivatives such as dioctyl phthalate, bis-2-ethylhexyl phthalate, dibenzyl phthalate, diisodecyl phthalate, didodecyl phthalate, and diundecyl phthalate, and isophthalic acid derivatives such as dioctyl isophthalate and dibutyl. Adipic acid derivatives such as adipate and dioctyl adipate, maleic acid derivatives such as dibutyl maleate, citric acid derivatives such as tributyl citrate, itaconic acid derivatives such as monobutyl itaconate, and oleic acid such as butyl oleate Derivatives, other tricresyl phosphates, tricsilyl phosphates, epoxidized soybean oil, epoxy resin plasticizers, and the like.

Examples of the lubricant or heat stabilizer include polyethylene wax, bisamide, stearic acid, zinc stearate, barium stearate, calcium stearate, and barium ricinoleate.

As said ultraviolet absorber, ultraviolet absorbers, such as a benzotriazole type, a benzoate type, a benzophenone type, a cyanoacrylate type, and a phenyl salicylate type, are mentioned, for example.

Examples of the pigment or dye include titanium oxide, silica, ultramarine blue, phthalocyanine blue and the like.

Hydrotalcite etc. are mentioned as said thermal insulation improving agent, for example. It is preferable to contain hydrotalcite for the performance improvement of the agricultural synthetic resin coating material.

These additives can be contained in a conventional content, such as 5 parts by mass or less per 100 parts by mass of synthetic resin.

In order to mix | blend the fluorine-containing compound of this invention, and also various additives if necessary, a synthetic compound and mixing technique can be used for the synthetic resin used as a base material. For example, it can mix by a ribbon blender, a Benbury mixer, a super mixer, other compounding machines, and a mixer. Then, it is filmed.

What is necessary is just to employ | adopt a well-known method, such as the melt extrusion method, the solution softening method, the calendering method, etc. in order to make a synthetic resin into a film.

0.01-0.5 mm is preferable and, as for the thickness of the synthetic resin film which is a coating material, 0.02-0.2 mm is especially preferable. Too thin will result in insufficient strength, and too thick will cause inconvenience in filming operations and subsequent handling (including cutting the film into a house shape, spreading in the house, etc.).

The synthetic resin additive of the present invention is excellent in both antifogging and antifogging persistence as well as the effect of suppressing the generation of fog when added to the agricultural coating material. Therefore, the agricultural coating material containing this synthetic resin additive is useful for plant cultivation of plants.

A synthesis example (Examples 1-6), Examples (Examples 7-12), and Comparative Examples (Examples 13-18) are given to the following and this invention is demonstrated in detail.

Example 1: Synthesis of Fluorine-containing Compound D

500 g of F (CF ₂ ) ₈ (CH ₂ ) ₃ OH is added in a powder state and 0.25 g of a zinc hexacyanocobaltate complex is added to the stainless pressure resistant autoclave. 546 g of propylene oxide (hereinafter referred to as PO hereinafter) is continuously introduced over 3 hours while the temperature is raised to 65 ° C and melted while stirring, and the temperature is raised to 80 ° C and maintained at 80 ° C.

After the reaction is completed, unreacted PO is distilled off under reduced pressure to obtain a crude product. Inorganic compounds were added by adding a chelating reagent and adding 1 mass part of adsorbents KW-1000 and KW-600 (both manufactured by Kyowa Chemical Co., Ltd., trade names) in order to 100 mass parts of the crude product, respectively, except for heavy metals in the solvent. Is adsorbed. Dehydration, filtration, and then drying to give the fluorine-containing compound D.

The hydroxyl value of the fluorine-containing compound D is 57.4 mgKOH / g. F (CF ₂ ) ₈ (CH ₂ ) ₃ O [CH ₂ CH (CH ₃ ) O] _n H ( _n ) by NMR spectra of the product ( ¹ H-NMR, ¹⁹ F-NMR and ¹³ C-NMR) The average value of is 8.6).

Example 2: Synthesis of Fluorine-containing Compound E

The reaction was carried out in the same manner as in Example 1, except that a mixture of PO / ethylene oxide (hereinafter referred to as EO) = 40/60 (mass ratio) was used instead of PO to obtain a fluorine-containing compound E.

The hydroxyl value of the fluorine-containing compound E is 56.8 mgKOH / g. According to the NMR spectrum of the product, F (CF ₂ ) ₈ (CH ₂ ) ₃ O [CH ₂ CH (CH ₃ ) O] _p (CH ₂ CH ₂ O) _q H (However, the sequence of PO and EO is random. The average value of p + q is 10 and p: q = 4: 6.

Example 3: Synthesis of Fluorine-containing Compound F

500 g of F (CF ₂ ) ₈ (CH ₂ ) ₃ OH is added in a powder state in a stainless pressure autoclave, 0.5 g of BF ₃ etherate and 250 g of dim as a diluent. It is dissolved with stirring, the temperature is raised to 30 ° C and 546 g of a mixture of tetrahydrofuran (hereinafter referred to as THF) / EO = 60/40 is continuously introduced over 3 hours while maintaining 30 ° C.

After 5 hours of thermal reaction, the crude product is obtained by distilling off the unreacted THF / EO and the solvent. An aqueous 10% sodium hydroxide solution is added to neutralize the acid, and then 1 mass parts of adsorbents KW-1000 and KW-600 (homologous) are added to 100 mass parts of the crude product, respectively, in order to adsorb the inorganic compound. Dehydration, filtration, and then drying to give the fluorine-containing compound F.

The hydroxyl value of the fluorine-containing compound F is 59.2 mgKOH / g. According to the NMR spectrum of the product, F (CF ₂ ) ₈ (CH ₂ ) ₃ O [CH ₂ CH ₂ CH ₂ CH ₂ O] _p (CH ₂ CH ₂ O) _q H (However, the sequence of THF and EO is random. The average value of p + q is 7.7 and p: q = 6: 4.

Example 4 Synthesis of Fluorine-containing Compound G

The reaction was carried out in the same manner as in Example 3, except that 573 g of PO was used instead of THF / EO to obtain a fluorine-containing compound G. The hydroxyl value of fluorine-containing compound G is 56.5 mg KOH / g. The NMR spectrum of the product confirmed the production of F (CF ₂ ) ₈ (CH ₂ ) ₃ O [CH ₂ CH (CH ₃ ) O] _n H (where the average value of n was 8.9).

Example 5 Synthesis of Fluorine-Containing Compound H

The reaction was carried out in the same manner as in Example 3, except that 546 g of EO was used instead of THF / EO to obtain a fluorine-containing compound H. The hydroxyl value of the fluorine-containing compound H is 56.3 mg KOH / g. The NMR spectrum of the product confirmed the production of F (CF ₂ ) ₈ (CH ₂ ) ₃ O (CH ₂ CH ₂ O) _n H (where the average value of n was 11.8).

Example 6 Synthesis of Fluorine-containing Compound I

The reaction was carried out in the same manner as in Example 3, except that F (CF ₂ ) ₈ CH ₂ CH ₂ CH (CH ₃ ) OH was used instead of F (CF ₂ ) ₈ (CH ₂ ) ₃ OH to obtain a fluorine-containing compound I. . The hydroxyl value of the fluorine-containing compound I is 56.3 mg KOH / g. The NMR spectrum of the product confirmed the formation of F (CF ₂ ) ₈ CH ₂ CH ₂ CH (CH ₃ ) O (CH ₂ CH ₂ O) _n H (where the average value of n was 11.5). In 0.01% aqueous solution of fluorine-containing compound I, the surface tension is 17.6 dyn / cm.

EXAMPLES 7-22

100 mass parts of polyvinyl chloride (average degree of polymerization = 1300), 50 mass parts of dioctylphthalate, 2 mass parts of Ba-Zn-based liquid stabilizer, and 1 mass part of Ba-Zn-based powder stabilizer are used as the basic composition. The antifogging agent and fluorine-containing compound of the kind and amount (unit: mass part) shown in Table 1 and Table 2 are mixed. The mixture was fed to a calender molding machine warmed to 180 ° C and filmed in a conventional manner to prepare 15 kinds of films (except Example 22) having a thickness of 0.075 mm. In addition, fluorine-containing compounds J, K, and L are shown in Table 3.

16 types of said 15 types of films and the commercially available antifogging agricultural polyvinyl chloride film (Example 22) of 0.075 mm in thickness which do not contain a fluorine-containing compound are evaluated.

The experimental greenhouse is assembled in an outdoor temperature control tank. The film is made by spreading the film on a frame 0.5 m high, 0.8 m wide and 0.4 m deep. The anti-fog and mist occurrence conditions are evaluated by the following method. The results are shown in Table 1 and Table 2.

[Kim Antifog Evaluation]

The test is started in September and the antifogging property of the film inside the experimental greenhouse is observed over 8 months. The anti-fog evaluation is based on the following criteria.

◎: No water droplets confirmed

O: Slightly attached water droplets

△: adhesion of water droplets is confirmed

×: Many droplets confirmed

××: Water droplets were observed over the entire surface

[Evaluation of the fog occurrence situation]

At the time when the temperature of morning and evening drops, the water temperature of the tank is set to 45 ° C., and the state of fog generated on the inner surface of the film in the experimental greenhouse is observed for about 2 hours. This observation is done twice in September and four times each month from October to April. The evaluation of the fog situation is based on the following criteria.

◎: Fog is not confirmed at all

O: Slight occurrence of fog

△: Fog occurrence is confirmed

×: Fog is remarkably confirmed

Yes 7 8 9 10 11 12 Fluorine-containing compounds DEFGHI 0.2 0.2 0.2 0.2 0.2 0.2 Outbreak situation of anti-fog fog ◎◎ ◎◎ ◎◎ ◎◎ ◎◎ ◎◎

Yes 13 14 15 16 17 18 Fluorine-containing compounds JKL 0.2 0.2 0.2 0.2 0.2 Outbreak situation of anti-fog fog OO △△ OO OO △△ X △

Fluorine-containing compound J: C ₈ F ₁₇ CH ₂ CH (OH) CH ₂ O (CH ₂ CH ₂ O) ₁₀ [CH ₂ CH (CH ₃ ) O] CH ₃ Fluorine-containing compound K: C ₉ F ₁₉ CON (CH ₃ ) (CH ₂ CH ₂ O) ₁₂ H fluorine-containing compound L: C ₈ F ₁₇ SO ₂ N (CH ₃ ) (CH ₂ CH ₂ O) ₁₀ H

Claims (5)

Synthetic resin additive containing a fluorine-containing compound represented by Formula 1 below: [Formula 1] R ^f -Q-O-(A-O) _n -R [In the meal, R ^f : polyfluoroalkyl group having 1 to 22 carbon atoms, Q: a straight or branched alkylene group having 3 to 5 carbon atoms, n: integer of 1 to 100, A: When one or more hydrogen atoms of a C2-C4 alkylene group or a C2-C4 alkylene group are substituted by monovalent aromatic hydrocarbon group, an alkoxy group, or a phenoxy group, and n is 2-100 A may be the same or different from each other, R is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms or an acyl group having 1 to 18 carbon atoms.]. The synthetic resin additive according to claim 1, wherein R is a hydrogen atom. The synthetic resin additive according to claim 1 or 2, wherein A is at least one group selected from ethylene, propylene and tetramethylene groups. The synthetic resin additive according to claim 1 or 2, wherein Q has 3 or 4 carbon atoms. The agricultural coating material which consists of a film of the synthetic resin containing the fluorine-containing compound of Claim 1 or 2, and containing no antifog.